CN110461823A - For in electrolyte composition or the salt as additive for electrode - Google Patents

For in electrolyte composition or the salt as additive for electrode Download PDF

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Publication number
CN110461823A
CN110461823A CN201880020602.XA CN201880020602A CN110461823A CN 110461823 A CN110461823 A CN 110461823A CN 201880020602 A CN201880020602 A CN 201880020602A CN 110461823 A CN110461823 A CN 110461823A
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compound
optionally substituted
alkyl
group
tautomer
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CN110461823B (en
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C·马莱
S·罗尚
A·拉弗勒-朗伯
S·于萨卡
K·扎吉布
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Quebec Power Co
Murata Manufacturing Co Ltd
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Quebec Power Co
Murata Manufacturing Co Ltd
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
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    • C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
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    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract

This disclosure relates to it is used as additive for electrode or the compound as the salt in electrolyte composition, and preparation method thereof.Most compounds are the imidazoles anionoid with sulfonyl or carbonyl, or the other nitrogen-containing groups being conjugated with various heterocycles or sulfonyl.Some electrochemical cells are also described, it includes the compounds as additive for electrode or as the salt in electrolyte composition.

Description

Salts for use in electrolyte compositions or as electrode additives
RELATED APPLICATIONS
This application claims priority to U.S. provisional application No.62/477,161, filed on 27/3/2017, the contents of which are incorporated herein by reference in their entirety for all purposes.
Technical Field
The technical field generally relates to salts for use in electrolyte compositions or as additives in electrode materials, and to methods of preparation. The technical field also relates to electrolyte compositions and electrode materials containing such salts and batteries containing them.
Background
Liquid, gel, or solid battery electrolytes typically comprise one or more lithium salts dissolved in a solvent and/or solvating polymer. Additives may be further added to improve the properties of the electrolyte, for example, its stability. Some of these salts may also be included in the electrode material to improve the ionic conductivity of the material. Among the salts commonly used, LiPF6(hexafluoro)Lithium phosphate) has interesting properties, but degrades in the presence of water to form hydrofluoric acid (HF). The HF formed can lead to dissolution of the cathode material.
Other salts have also been developed, including LiFSI and LiTFSI and LiTDI. These salts also have their own disadvantages. For example, TFSI-anions are very reactive and often lead to corrosion of the aluminum current collector even at low voltages. Neither LiFSI nor LiTFSI is recommended for high voltage applications and is expensive. Litid is more stable than the other two, but is very hygroscopic and has conductivity and solubility problems.
It is therefore highly desirable to develop new salts for use in electrolyte compositions or as additives in electrode materials, e.g. having one or more of the following advantages over the currently used salts: improved ionic conductivity, reduced production costs, improved solubility in electrolyte solvents, and/or the formation of a more conductive SEI.
Disclosure of Invention
According to one aspect, compounds, such as salts, are described herein for use in electrolyte compositions and/or as additives in electrode materials. In one embodiment, the compound is as defined in formula I:
wherein,
R1and R2Independently selected from H, F, CN, NO2Optionally substituted alkyl, preferably CN;
R3selected from NHSO2R4，NHSO2OR4，SO2NHSO2R4，SO2NHSO2OR4Or an optionally substituted heterocycle;
R4selected from fluorine, optionally substituted C1-6Alkyl and optionally substituted C6An aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal and n is 1 or 2, for example M is an alkali metal, an alkaline earth metal, for example,m is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
In one embodiment, R3Is NHSO2R4. In another embodiment, R3Is NHSO2OR4. For example, R4Is C substituted by at least one of fluorine and alkoxy1-6Alkyl, or R4Is C substituted by at least one fluorine atom6And (4) an aryl group. In another embodiment, R3Is a heterocyclic ring. In another embodiment, R1And R2Is CN, or R1And R2Are all CN.
In a further embodiment, the compound of formula I is a compound selected from the group consisting of:
or a tautomer thereof.
According to another embodiment, the compound is as defined in formula II:
wherein,
R5selected from optionally substituted C1-6Alkyl and optionally substituted C6An aryl group; and
R6selected from optionally substituted C1-6Alkyl and optionally substituted C6An aryl group;
(Mn+ )1/nis a metal cation, wherein M is a metal, n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metal, e.g. M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
In one embodiment, R5Is unsubstituted C1-6An alkyl group. In another embodiment, R5Is fluorinated C1-6An alkyl group. In further embodiments, R6Is fluorinated C1-6An alkyl group. In yet another embodiment, R6Is fluorinated C6And (4) an aryl group. In yet another embodiment, R5And R6At least one of which is optionally substituted C6Aryl (e.g. C substituted by one or more fluorine atoms6Aryl). In other embodiments, the compound has formula II, with the proviso that when R is6When it is trifluoromethyl, then R5Is not methyl or trifluoromethyl.
In a further embodiment, the compound of formula II is a compound selected from the group consisting of:
or a tautomer thereof.
According to a further embodiment, the compound is as defined in formula III:
wherein,
R7selected from fluorine atoms and optionally substituted C1-6An alkyl group; and
L1is a covalent bond or is selected from optionally substituted C1-6Alkyl and optionally substituted C6A linker for an aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal, n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metal, e.g. M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
In one embodiment, R7Is a fluorine atom. In another embodiment, R7Selected from fluorine substituted C1-6An alkyl group. In a further embodiment, L1Is a covalent bond or L1Is selected from optionally substituted C6A linker for aryl.
In a further embodiment, the compound of formula III is a compound selected from the group consisting of:
or a tautomer thereof.
According to another embodiment, the compound is as defined in formula IV:
wherein,
X1is a carbon or nitrogen atom;
when X is present1When it is a carbon atom, R8And R9Each independently F, CN or optionally substituted C1-6An alkyl group; or
When X is present1When it is a nitrogen atom, R8Is absent and R9Is optionally substituted SO2Alkyl or optionally substituted C1-6An alkyl group;
(Mn+)1/nis a metal cation, wherein M is a metal, n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metal, e.g. M is Li, Na or K, or M is Li and n is 1;
m is an integer selected from 0 or 1;
or a tautomer thereof.
In one embodiment, X1Is a carbon atom. In one embodiment, R8And R9Is different. Or, R8And R9The same is true. In another embodiment, R8And R9At least one of which is CN or optionally substituted C1-6An alkyl group. In one embodiment, R8And R9Are all CN or optionally substituted C1-6Alkyl, or R8And R9Are all CN, or R8And R9All being fluorine substituted C1-6An alkyl group. In another embodiment, X1Is a nitrogen atom. For example, X1Is a nitrogen atom, R9Is fluorine substituted SO2Alkyl (e.g. SO)2CF3). In another implementationIn the scheme, m is 0. In another embodiment, m is 1.
In a further embodiment, the compound of formula IV is a compound selected from the group consisting of:
or a tautomer thereof.
According to another embodiment, the compound is as defined in formula V:
wherein R is1、R2、R8、R9、X1M and n are as previously defined, or R8And R9Is absent and X1Is an oxygen atom;
or a tautomer thereof.
In one embodiment, R1And R2Is CN. For example, R1And R2Are all CN. In another embodiment, X1Is a carbon atom. For example, X1Is a carbon atom and R8And R9Are all CN or optionally substituted C1-6Alkyl, or X1Is a carbon atom and R8And R9Are all CN, or X1Is a carbon atom and R8And R9All fluorine substituted C1-6An alkyl group. In another embodiment, X1Is a nitrogen atom. For example, X1Is a nitrogen atom and R9Is fluorine substituted SO2Alkyl (e.g. SO)2CF3)。
In a further embodiment, the compound of formula V is a compound selected from the group consisting of:
or a tautomer thereof.
In one embodiment, a compound according to any one of the preceding embodiments is described, wherein M is Li and n is 1. In another embodiment, the compounds are as defined herein and are disalt (e.g., a dianion that forms a salt with two alkali metal anions, where applicable). For example, compounds of formulas I, IV and V, the compounds may contain an additional anion on the second nitrogen atom. For example, compounds E1 to E4 may form disalts, e.g., for compound E2:
further contemplated is the free form of any salt mentioned herein.
According to another aspect, the present technology relates to an electrode material comprising as an additive a compound as defined herein and at least one electrochemically active material.
According to another aspect, the present technology relates to electrolyte compositions comprising a compound as described herein. For example, the electrolyte composition further comprises a compatible solvent. In another example, the electrolyte composition further comprises a compatible solvating polymer.
In another aspect, it also relates to an electrochemical cell comprising an electrolyte, an electrode and a counter electrode, wherein at least one of the electrode or counter electrode comprises an electrode material comprising as an additive a compound as defined herein, and at least one electrochemically active material. Alternatively, it relates to an electrochemical cell comprising an electrolyte composition comprising a compound as defined herein, an electrode and a counter electrode. In one embodiment, the electrochemical cell comprises a compound as defined herein in the electrolyte composition and in at least one electrode material. In one embodiment, the electrochemical cell is contained in a battery, electrochromic device, or capacitor. For example, the battery is a lithium battery or a lithium ion battery. In other examples, the battery is a sodium or potassium battery.
According to another aspect, use of an electrochemical cell as defined herein in an electric or hybrid vehicle or in a ubiquitous IT installation is described.
Other features and advantages of the present technology will be better understood upon reading the following description.
Detailed Description
Compounds (e.g., salts) intended for use as additives to electrode materials or as components of electrolyte compositions are described herein. The compound is one of formulae I to V as defined herein. Exemplary compounds are also described, but should not be construed as limiting the broader scope of the formula.
Thus, the compound may be as defined in formula I:
wherein,
R1and R2Independently selected from H, F, CN, NO2Optionally substituted alkyl, preferably CN;
R3selected from NHSO2R4，NHSO2OR4，SO2NHSO2R4，SO2NHSO2OR4Or an optionally substituted heterocycle;
R4selected from fluorine, optionally substituted C1-6Alkyl and optionally substituted C6An aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal, n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metal, e.g. M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
For example, R3Is NHSO2R4Or R is3Is NHSO2OR4. For example, R3Is NHSO2R4Or NHSO2OR4And R is4Is C substituted by at least one of fluorine and alkoxy1-6Alkyl, or R4Is C substituted by at least one fluorine atom6And (4) an aryl group. In another example, R3Is C5-6Heterocycles (e.g. non-aromatic C connected via a nitrogen atom)5-6Heterocycles, such as maleimide). In another embodiment, R1And R2Is CN, or R1And R2Are all CN.
Examples of compounds of formula I include, but are not limited to, compounds a1 to a5, as defined above, or tautomers thereof.
The compound may also be as defined in formula II:
wherein,
R5selected from optionally substituted C1-6Alkyl and optionally substituted C6An aryl group; and
R6selected from optionally substituted C1-6Alkyl and optionally substituted C6An aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal, n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metal, e.g. M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
For example, R5Is unsubstituted C1-6Alkyl (e.g., methyl, ethyl, propyl, isopropyl, etc.), or R5Is fluorinated C1-6Alkyl (e.g., trifluoromethyl, etc.). In another example, R6Is fluorinated C1-6Alkyl (e.g., trifluoromethyl, etc.) or R6Is fluorinated C6Aryl (e.g., pentafluorophenyl and the like). Other examples include compounds of formula II, wherein R5And R6At least one of which is optionally substituted C6And (4) an aryl group. In other examples, the compound has formula II, with the proviso that when R is6When it is trifluoromethyl, then R5Is not methyl or trifluoromethyl.
Examples of compounds of formula II include, but are not limited to, compounds B1 to B4, as defined herein, or tautomers thereof. For example, the compound is compound B3 or B4, as defined herein, or a tautomer thereof.
The compound may also be as defined in formula III:
wherein,
R7selected from fluorine atoms and optionally substituted C1-6An alkyl group; and
L1is a covalent bond or is selected from optionally substituted C1-6Alkyl and optionally substituted C6A linker for an aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal, n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metal, e.g. M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
For example, R7Is a fluorine atom or R7Selected from fluorine substituted C1-6An alkyl group. According to some examples, L1Is a covalent bond. According to other examples, L1Is selected from optionally substituted C6A linker for aryl.
Examples of compounds of formula III include, but are not limited to, compounds C1 to C4, as defined herein, or tautomers thereof.
The compound may be further defined as in formula IV:
wherein,
X1is a carbon or nitrogen atom;
when X is present1When it is a carbon atom, R8And R9Each independently F, CN or optionally substituted C1-6An alkyl group; or
When X is present1When it is a nitrogen atom, R8Is absent and R9Is optionally substituted SO2Alkyl or optionallySubstituted C1-6An alkyl group;
(Mn+)1/nis a metal cation, wherein M is a metal, n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metal, e.g. M is Li, Na or K, or M is Li and n is 1;
m is an integer selected from 0 or 1;
or a tautomer thereof.
In some examples, X1Is a carbon atom. When X is present1When it is a carbon atom, R8And R9May be the same or different. For example, X1Is a carbon atom, R8And R9At least one of which is CN or optionally substituted C1-6An alkyl group. For example, X1Is a carbon atom, R8And R9Are all CN or optionally substituted C1-6Alkyl, or R8And R9Are all CN, or R8And R9All fluorine substituted C1-6An alkyl group. According to other examples, X1Is a nitrogen atom. For example, X1Is a nitrogen atom, R8Is absent, R9Is fluorine substituted SO2Alkyl (e.g. SO)2CF3). In one example, m is 0. In another example, m is 1.
Examples of compounds of formula IV include, but are not limited to, compounds D1 to D6, as defined herein, or tautomers thereof.
The compounds may also be defined as in formula V:
wherein R is1、R2、R8、R9、X1M and n are as defined above, or R8And R9Is absent, X1Is an oxygen atom;
or a tautomer thereof.
For example, R1And R2Is CN, or R1And R2Are all CN. In some examples, X1Is a carbon atom. For example, X1Is a carbon atom, R8And R9Are all CN or optionally substituted C1-6Alkyl, or X1Is a carbon atom, R8And R9Are all CN, or X1Is a carbon atom, R8And R9All fluorine substituted C1-6An alkyl group. In other examples, X1Is a nitrogen atom. For example, X1Is a nitrogen atom, R9Is fluorine substituted SO2Alkyl (e.g. SO)2CF3)。
Examples of compounds of formula V include, but are not limited to, compounds E1 to E4, as defined herein, or tautomers thereof.
According to one example, the compound is as defined in any one of formulas I to V, wherein M is Li and n is 1. In another embodiment, the compounds are as defined herein and are disalt (e.g., a dianion that forms a salt with two alkali metal anions, where applicable). For example, compounds of formulas I, IV and V, the compounds may contain an additional anion on the second nitrogen atom. Further contemplated is the free form of any salt mentioned herein.
As used herein, the term "alkyl" refers to saturated hydrocarbons having 1 to 16 carbon atoms, including linear or branched alkyl groups. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, and the like. When an alkyl group is located between two functional groups, the term alkyl also includes alkylene groups such as methylene, ethylene, propylene, and the like. The term "C1-CnAlkyl "refers to an alkyl group having from 1 to the indicated" n "carbon atoms.
The term "alkoxy" as used herein refers to an alkyl group having an oxygen atom attached thereto. Representative alkoxy groups include groups having from 1 to about 6 carbon atoms such as methoxy, ethoxy, propoxy, tert-butoxy and the like. Examples of alkoxy groups include methoxy, ethoxy, isopropoxy, propoxy, butoxy, pentyloxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy and the like. The term alkoxy includes unsubstituted or substituted alkoxy and the like, as well as haloalkoxy.
The term "aryl" refers to an aromatic group having 4n +2 pi (pi) electrons, where n is an integer from 1 to 3, in a conjugated monocyclic or polycyclic system (fused or unfused) and having 6 to 14 ring atoms. The polycyclic ring system includes at least one aromatic ring. The aryl groups may be directly linked, or via C1-C3An alkyl linkage (also known as arylalkyl or aralkyl). Examples of aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, 1-phenylethyl, tolyl, naphthyl, biphenyl, terphenyl, indenyl, benzocyclooctenyl, benzocycloheptenyl, azulenyl, acenaphthenyl, fluorenyl, phenanthrenyl, anthracenyl, and the like. The term aryl includes both unsubstituted aryl and substituted aryl. The term "C6-CnAryl "refers to an aryl group having from 6 to the indicated" n "carbon atoms in the ring structure.
The term "heterocycle" or "heterocyclic" includes heterocycloalkyl and heteroaryl. Examples of heterocycles include, but are not limited to, acridinyl, azocinyl, benzimidazolyl, benzofuranyl, benzothienyl, benzothiophenyl, benzofuranyl, and benzothiophenylAzolyl, benzothiazolyl, benzotriazolyl, benzotetrazolyl, benzisoxazolylAzolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4. alpha. H-carbazolyl, carbolinyl, chromanyl, benzopyranyl, cinnolinyl, decahydroquinolinyl, 2H, 6H-1,5, 2-dithiazinyl, dihydrofuran [2,3-b]Tetrahydrofuran, furyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, (E) -8-indol-1-yl-2, 6-dimethyloct-7-en-2-ol (indolenyl), indolinyl, indolizinyl, indolyl, 3H-indolyl, isobenzofuryl, isobenzodihydropyranyl, isoindolyl, isoindolinyl, isoindolyl, isoquinolyl, isothiazolyl, isoindazolylOxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl,oxadiazolyl, 1,2,3-Oxadiazolyl, 1,2,4-Oxadiazolyl, 1,2,5-Oxadiazolyl, 1,3,4-(ii) a diazolyl group,an oxazolidinyl group, which is a group of,the group of azolyl groups,oxazolidinyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, thioxanthyl, phenoxathiinylAzinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridoAzole, pyridoimidazole, pyridothiazole, pyridyl (pyridinyl), pyridyl (pyridil), pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl, quinuclidinyl, tetrakisHydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 6H-1,2, 5-thiadiazinyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thieno-thiazolyl, thienoOxazolyl, thienoimidazolyl, thiophenyl, triazinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, 1,2, 5-triazolyl, 1,3, 4-triazolyl, xanthenyl and the like. The term heterocycle includes both unsubstituted heterocyclic groups and substituted heterocyclic groups.
The term "substituted" when combined with any of the foregoing groups refers to a group substituted at one or more positions with a substituent such as cyano, halogen, nitro, trifluoromethyl, lower alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, lower alkoxy, aryloxy, benzyloxy, benzyl, sulfonyl, sulfonate, sulfonamide, phosphonato, phosphiniato, oxo, and the like. Any of the above substituents may be further substituted if permitted, for example, if the group contains an alkyl, alkoxy, aryl or other group.
Also described is an electrode material comprising as an additive a compound as defined herein and at least one electrochemically active material. The electrochemically active material may be a material for a negative electrode. Alternatively, the electrochemically active material may be a material for a positive electrode. Examples of electrochemically active materials include, but are not limited to, titanates and lithium titanates (e.g., TiO)2、Li2TiO3、Li4Ti5O12、H2Ti5O11、H2Ti4O9Or combinations thereof), lithium and metal phosphates (e.g., LiM' PO)4Where M' is Fe, Ni, Mn, Co, or combinations thereof), vanadium oxides (e.g., LiV)3O8、V2O5、LiV2O5Etc.), and other lithium and metal oxides, such as LiMn2O4、LiM”O2(M 'is Mn, Co, Ni or a combination thereof), Li (NiM' ")O2(M' "is Mn, Co, Al, Fe, Cr, Ti, Zr, etc., or combinations thereof), or combinations thereof. For example, the active material is selected from the group consisting of lithium iron phosphate (LFP), lithium manganese iron phosphate (LMFP), Lithium Titanate (LTO), graphite, and lithium nickel manganese cobalt oxide (NMC). The particles may be newly formed or of commercial origin, in the form of microparticles or nanoparticles and may also contain a carbon coating.
The electrode material may also optionally contain additional components such as conductive materials, inorganic particles, glass or ceramic particles, and the like. Examples of the conductive material include carbon black, KetjenTMBlack, acetylene black, graphite, graphene, carbon fibers, nanofibers (e.g., VGCF), or nanotubes, or combinations thereof. The electrode material may further comprise a binder. Examples of the binder include water-soluble binders such as SBR (styrene-butadiene rubber), NBR (butadiene acrylonitrile rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber), and the like, and cellulose-based binders such as carboxyalkyl cellulose, hydroxyalkyl cellulose, and combinations thereof, or any combination of two or more of these. For example, the carboxyalkyl cellulose may be carboxymethyl cellulose (CMC) or carboxyethyl cellulose. Hydroxypropyl cellulose is an example of hydroxyalkyl cellulose. Other examples of binders include fluoropolymer binders, such as PVDF and PTFE, and ionically conductive polymer binders, such as block copolymers composed of at least one lithium ion solvating segment and at least one crosslinkable segment.
According to another aspect, the present technology relates to electrolyte compositions comprising a compound as described herein. The electrolyte may be a liquid, gel, or solid polymer electrolyte, and in the case of a lithium or lithium-ion electrochemical cell, is conductive to lithium ions. For example, the electrolyte composition further comprises a compatible solvent. In another example, the electrolyte composition further comprises a compatible solvating polymer.
For example, the electrolyte is prepared by dissolving one or more compounds of the present invention in an appropriate electrolyte solvent or solvating polymer to prepare a polymer electrolyte. For use in lithium and lithium ion batteries, the compound as the lithium salt may be dissolved in a suitable concentration, for example 0.05 to 3 mol/L. For other types of batteries, other salts of the compounds of the invention should be dissolved, e.g. sodium salts for sodium batteries, magnesium salts for magnesium batteries, etc.
Non-limiting examples of the electrolyte solvent include organic solvents such as ethers, carbonates, cyclic carbonates, aliphatic carboxylates, aromatic carboxylates, phosphates, sulfites, nitriles, amides, alcohols, sulfoxides, sulfolane, nitromethane, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1, H) -pyrimidinone, 3-methyl-2-Oxazolidinones, or mixtures thereof. In a particular example, the solvent may also be an aqueous solvent, i.e. water or a mixture comprising water.
Examples of solvents include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, γ -butyrolactone, glyme, diglyme, triglyme, tetraglyme, sulfolane, tetraethylsulfonamide, acetonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2-methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, malononitrile, and combinations thereof. Various additives may also be included in the electrolyte composition to improve its performance.
Non-limiting examples of polymers for electrolytes (e.g., gels or solids) include poly (ethylene oxide) and copolymers and block copolymers thereof, poly (propylene oxide) and copolymers and block copolymers thereof, poly (dimethylsiloxane) and copolymers and block copolymers thereof, poly (alkylene carbonate) and copolymers and block copolymers thereof, poly (alkylene sulfone) and copolymers and block copolymers thereof, poly (alkylene sulfonamide) and copolymers and block copolymers thereof, polyurethanes and copolymers and block copolymers thereof, poly (vinyl alcohol) and copolymers and block copolymers thereof, and combinations thereof. In addition, branched or crosslinked solvating polymers may also be included. Various additives may also be included in the polymer electrolyte composition to improve its performance.
The electrochemical cell described herein comprises an electrolyte, an electrode and a counter electrode, wherein at least one of the electrode or counter electrode comprises an electrode material comprising as an additive a compound as defined herein and at least one electrochemically active material as defined above. Alternatively, it relates to an electrochemical cell comprising an electrolyte composition comprising a compound as defined herein, an electrode and a counter electrode. In one embodiment, the electrochemical cell comprises a compound as defined herein in the electrolyte composition and in at least one electrode material. In one embodiment, the electrochemical cell is contained in a battery, electrochromic device, or capacitor. For example, the battery is a lithium battery or a lithium ion battery. In other examples, the battery is a sodium battery or a potassium battery.
According to another aspect, the use of an electrochemical cell as defined herein in an electric or hybrid vehicle or in a ubiquitous IT device is described.
Examples
The following non-limiting examples are illustrative embodiments and should not be construed to further limit the scope of the present application.
Example 1: preparation of Compounds of formula I
a) Compound A1
2-amino-1H-imidazole-4, 5-dinitrile (1.1 equiv.), trifluorosulfonyl chloride (1 equiv.), lithium carbonate (2 equiv.) and N' N-Dimethylaminopyridine (DMAP) (0.25 equiv.) were introduced into a Schlenk flask. By vacuum-N2The cycle deaerates the solids. Anhydrous acetone (1M) was added and the suspension was stirred vigorously and heated at reflux overnight. The reaction mixture was cooled to room temperature. Distilled water was added and the solution was extracted with dichloromethane. The combined organic layers were washed with water and acidic water, using MgSO4Dried and filtered. The solution is added inFiltered to remove inorganic residues. The organic solution was concentrated under reduced pressure until dry. The solid residue was purified by silica gel chromatography using hexane/ethyl acetate (1/1) as eluent. After evaporation a crystalline yellow solid was isolated. The yellow solid was then dissolved in water and lithium hydroxide monohydrate added until a slight excess of base was detected with pH paper. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
b) Compound A2
2,4, 6-trichloro- [1,3,5 ]]-triazine (1 eq) was added to a solution of sulfonic acid (1 eq) in anhydrous acetone at room temperature, followed by dropwise addition of trimethylamine (1 eq). The solution was stirred vigorously and heated at 90 ℃ overnight. The reaction mixture was cooled to room temperature and 2-amino-1H-imidazole-4, 5-dinitrile (1.2 equivalents), DMAP (0.25 equivalents) and lithium carbonate (2 equivalents) were added under nitrogen. The mixture was stirred vigorously and heated at 90 ℃ for 2 days. The reaction mixture was cooled to room temperature. Distilled water was added and the solution was extracted with dichloromethane. The combined organic layers were washed with water and acidic water, over MgSO4Dried and filtered. The solution is added inFiltered to remove inorganic residues. The organic solution was concentrated under reduced pressure until dry. The solid residue was purified by silica gel chromatography using hexane/ethyl acetate (1/1) as eluent. A crystalline yellow solid was isolated. The yellow solid was then dissolved in water and lithium hydroxide monohydrate added until a slight excess of base was detected with pH paper. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
c) Compound A3
2-amino-1H-imidazole-4, 5-dinitrile (1.1 equiv.), pentafluorosulfonyl chloride (1 equiv.), lithium carbonate (2 equiv.) and N' N-Dimethylaminopyridine (DMAP) (0.25 equiv.) were introduced into a Schlenk flask. By vacuum-N2The cycle deaerates the solids. Anhydrous acetone (1M) was added and the suspension was stirred vigorously and heated under reflux. The reaction mixture was cooled to room temperature. Distilled water was added and the solution was extracted with dichloromethane. The combined organic layers were washed with water and acidic water, over MgSO4Dried and filtered. The solution is added inFiltered to remove inorganic residues. The organic solution was concentrated under reduced pressure until dry. The solid residue was purified by silica gel chromatography using hexane/ethyl acetate (1/1) as eluent. A crystalline yellow solid was isolated. The yellow solid was then dissolved in water and lithium hydroxide monohydrate added until a slight excess of base was detected with pH paper. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
d) Compound A4
Step 1: a THF solution of 2-methoxyethyl-1-ol was added dropwise to a THF solution of sulfuryl chloride (1.2 equivalents) at-75 deg.C. The reaction mixture was warmed to room temperature. The solution was concentrated to dryness under reduced pressure. The obtained colorless oil was used without purification.
Step 2: 2-amino-1H-imidazole-4, 5-dinitrile (1.1 equiv.), 2-methoxyethyl-1-sulfonyl chloride (1 equiv.), lithium carbonate (2 equiv.) and N' N-Dimethylaminopyridine (DMAP) (0.25 equiv.) were introduced into a Schlenk flask. By vacuum-N2The cycle deaerates the solids. Anhydrous acetone (1M) was added and the suspension was stirred vigorously and heated at reflux overnight. The reaction mixture was cooled to room temperature. Distilled water was added, and the resulting solution was extracted with dichloromethane. The combined organic layers were washed with water and acidic water over MgSO4Dried and filtered. The resulting organic solution was concentrated to dryness under reduced pressure. The brown oil obtained was purified by silica gel chromatography. A yellow oil was separated. The resulting compound is converted to its lithium salt by dissolving in water and adding lithium hydroxide. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
e) Compound A5
Dissolving 2-amino-1H-imidazole-4, 5-dinitrile and maleic anhydride in 1, 4-bisIn an alkane. The solution was heated at 150 ℃ for 10 hours by microwave activation. The mixture was precipitated in cold ether and filtered. The yellowish filtrate was evaporated and a pale yellow superabsorbent solid was isolated. The solid was then dissolved in water and lithium hydroxide monohydrate added until slightly detected with pH paperAn excess of base. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
Example 2: preparation of Compounds of formula II
a) Compound B1
Acetamide (1.1 eq), trifluorosulfonyl chloride (1 eq), lithium carbonate (2 eq) and N' N-Dimethylaminopyridine (DMAP) (0.25 eq) were introduced into a Schlenk flask. By vacuum-N2The cycle deaerates the solids. Anhydrous acetone (1M) was added and the suspension was stirred vigorously and heated at reflux overnight. The reaction mixture was cooled to room temperature. Distilled water was added and the solution was extracted with dichloromethane. The combined organic phases were washed with water and MgSO4Dried and filtered. The organic solution was concentrated to dryness under reduced pressure. The crude oil was then dissolved in water and lithium hydroxide monohydrate was added until a slight excess of base was detected with pH paper. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
b) Compound B2
Trifluoroacetamide (1.1 eq), trifluorosulfonyl chloride (1 eq), lithium carbonate (2 eq) and N' N-Dimethylaminopyridine (DMAP) (0.25 eq) were introduced into a Schlenk flask. By vacuum-N2The cycle deaerates the solids. Adding anhydrous waterAcetone (1M) and the suspension was stirred vigorously and heated at reflux overnight. The reaction mixture was cooled to room temperature. Distilled water was added and the solution was extracted with dichloromethane. The combined organic layers were washed with water and MgSO4Dried and filtered. The organic solution was concentrated to dryness under reduced pressure. The crude oil was then dissolved in water and lithium hydroxide monohydrate was added until a slight excess of base was detected with pH paper. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
c) Compound B3
Acetamide (1.1 eq), pentafluorobenzenesulfonyl chloride (1 eq), lithium carbonate (2 eq) and N' N-Dimethylaminopyridine (DMAP) (0.25 eq) were introduced into a Schlenk flask. By vacuum-N2The cycle deaerates the solids. Anhydrous acetone (1M) was added and the suspension was stirred vigorously and heated at reflux overnight. The reaction mixture was cooled to room temperature, distilled water was added, and the solution was extracted with dichloromethane. The combined organic layers were washed with water and MgSO4Dried and filtered. The crude solid was then dissolved in water and lithium hydroxide monohydrate added until a slight excess of base was detected with pH paper. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
d) Compound B4
Trifluoroacetamide (1.1 eq), pentafluorobenzenesulfonyl chloride (1 eq), lithium carbonate (2 eq) and N' N-Dimethylaminopyridine (DMAP) (0.25 eq) were introduced into a Schlenk flask. By vacuum-N2The cycle deaerates the solids. Anhydrous acetone (1M) was added and the suspension was stirred vigorously and heated at reflux overnight. The reaction mixture was cooled to room temperature, distilled water was added, and the solution was extracted with dichloromethane. The combined organic layers were washed with water and MgSO4Dried and filtered. The crude solid was then dissolved in water and lithium hydroxide monohydrate added until a slight excess of base was detected with pH paper. The solution was concentrated to dryness by distillation under reduced pressure. The solid was suspended in diethyl carbonate (DEC) and stirred at room temperature overnight. Passing the solution throughAnd the clear solution was concentrated under reduced pressure and dried in a vacuum oven for 24 hours.
Example 3: preparation of Compounds of formula III
Compound C1
Step 1: sulfonamide, lithium carbonate (1 eq) and 4-nitrophenyl triflate were mixed and ground with a mortar and pestle. The molten mixture was stirred at 180 ℃ for 1 hour under nitrogen. Deionized water was added to the hot mixture with vigorous stirring. Insoluble suspended solids were removed by filtration. The water was removed under reduced pressure. The solid was washed with cold THF, ethyl acetate and the white solid was filtered. The yellow filtrate was evaporated under reduced pressure and the yellow solid was dried under vacuum at 40 ℃ overnight.
Step 2: the solid THF solution of step 1 was added to the 1, 4-bis-maleic anhydride solutionAn alkane solution, and the resulting mixture was stirred at room temperature for 12 hours. The corresponding carboxylic acid was isolated by filtration as a white solid and dried under vacuum at 60 ℃ for 4 hours.
Step 3: the acetic anhydride solution of the carboxylic acid of step 2 and sodium acetate were heated at 70 ℃ for 3 hours. Then, the solution was poured into an excess of diethyl ether to complete the precipitation. The resulting precipitate was isolated by filtration and dried under vacuum at 60 ℃ overnight.
Example 4: preparation of Compounds of formulae IV and V
a) Compound E2 (free form)
A solution of diaminomaleonitrile (1.0g, 4.625mmol) and anhydrous dimethylformamide (10mL) was added to an inert reactor. The compound 2- [ bis (methylthio) methylene ] malononitrile (DM3) (0.787g, 4.625mmol) was added and the mixture was stirred at 120 ℃ for 16 h. The solvent and volatile compounds were removed under vacuum. The resulting product was purified by silica gel chromatography using a mixture of ethyl acetate and hexane as eluent.
b) Compound D3 (free form)
A solution of compound DM3(0.500g, 2.94mmol) in methanol (50mL) was inserted into an inert reactor (pressure bomb). Ammonia (0.500g, 29.4mmol) was added and the reaction mixture was stirred at 70 ℃ for 16 h. The solvent and volatile compounds were removed under vacuum. The resulting compound (DM 3-NH)2) It was used without further purification.
Compound DM3-NH2(0.500g, 4.63mmol) in THF (50mL) was introduced into the inert reactionIn the device. Oxalyl chloride (0.587g, 4.63mmol) was added and the reaction mixture was stirred at room temperature for 16 h. The solvent and volatile compounds were removed under vacuum. The product was purified by recrystallization from alcohol.
c) Compound E4 (free form)
A solution of diaminomaleonitrile (8.0g, 74.0mmol) in anhydrous tetrahydrofuran (250mL) was introduced into an inert reactor and the solution degassed. Phosgene (7.32g, 74.0mmol) was added and the mixture was stirred for 1 hour. Ethanethiol (14.9g, 148.0mmol) was then added and the mixture was stirred for a further 16 hours. The solvent and volatile compounds were removed under vacuum. Acetone (100mL) and 5 drops of 12M HCl were added and the mixture was heated at 120 ℃ for 16 hours until a complete color change from orange to off-white was observed. The product is an off-white powder.
Example 5: conductivity of the selected salt
The conductivity measurements were carried out using a biological conductivity meter (model MCS-10) using platinum cells (type HTCC: parallel plate platinum on glass support). The salt was dried overnight in a vacuum oven at 70 ℃ before use and PC/EMC/DMC (4/3/3) or distilled water was used as solvent. LiCl (in water) or LiPF6The solution (in PC/EMC/DMC) was used as reference.
TABLE 1 conductivity results
In its dilithium salt form.
Many modifications may be made to any embodiment described above without departing from the scope of the present invention. Any reference, patent or scientific literature document mentioned in this application is hereby incorporated by reference in its entirety for all purposes.

Claims (56)

1. A compound as defined in formula I:
wherein,
R1and R2Independently selected from H, F, CN, NO2Optionally substituted alkyl, preferably CN;
R3selected from NHSO2R4、NHSO2OR4、SO2NHSO2R4、SO2NHSO2OR4Or an optionally substituted heterocycle;
R4selected from fluorine, optionally substituted C1-6Alkyl and optionally substituted C6An aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal and n is 1 or 2, for example M is an alkali metal, an alkaline earth metal, for example M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
2. The compound of claim 1, wherein R3Is NHSO2R4。
3. The compound of claim 1, wherein R3Is NHSO2OR4。
4. A compound according to claim 2 or 3, wherein R4Is C substituted by at least one of fluorine and alkoxy1-6An alkyl group.
5. A compound according to claim 2 or 3, wherein R4Is C substituted by at least one fluorine atom6And (4) an aryl group.
6. The compound of claim 1, wherein R3Is a heterocyclic ring.
7. The method of any one of claims 1 to 6Compound (I) wherein R1And R2Is CN.
8. The compound of claim 7, wherein R1And R2Are all CN.
9. The compound of claim 1, wherein the compound is selected from the group consisting of:
or a tautomer thereof.
10. A compound as defined in formula II:
wherein,
R5selected from optionally substituted C1-6Alkyl and optionally substituted C6An aryl group; and
R6selected from optionally substituted C1-6Alkyl and optionally substituted C6An aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal and n is 1 or 2, for example M is an alkali metal, an alkaline earth metal, for example M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
11. The compound of claim 10, wherein R5Is unsubstituted C1-6An alkyl group.
12. The compound of claim 10, wherein R5Is fluorinated C1-6An alkyl group.
13. The compound of any one of claims 10-12, wherein R6Is fluorinated C1-6An alkyl group.
14. The compound according to any one of claims 10 to 12, wherein R6Is fluorinated C6And (4) an aryl group.
15. The compound of claim 10, wherein the compound is selected from the group consisting of:
or a tautomer thereof.
16. The compound of claim 15, wherein the compound is selected from the group consisting of:
17. a compound as defined in formula III:
wherein,
R7selected from fluorine atoms and optionally substituted C1-6An alkyl group; and
L1is a covalent bond or is selected from optionally substituted C1-6Alkyl and optionally substituted C6A linker for an aryl group;
(Mn+)1/nis a metal cation, wherein M is a metal and n is 1 or 2, for example M is an alkali metal, an alkaline earth metal, for example M is Li, Na or K, or M is Li and n is 1;
or a tautomer thereof.
18. The compound of claim 17, wherein R7Is a fluorine atom.
19. The compound of claim 17, wherein R7Selected from fluorine substituted C1-6An alkyl group.
20. The compound of any one of claims 17-19, wherein L1Is a covalent bond.
21. The compound of any one of claims 17-19, wherein L1Is selected from optionally substituted C6A linker for aryl.
22. The compound of claim 17, wherein the compound is selected from the group consisting of:
or a tautomer thereof.
23. A compound as defined in formula IV:
wherein,
X1is a carbon or nitrogen atom;
when X is present1When it is a carbon atom, R8And R9Each independently F, CN or optionally substituted C1-6An alkyl group; or
When X is present1When it is a nitrogen atom, R8Is absent and R9Is optionally substituted SO2Alkyl or optionally substituted C1-6An alkyl group;
(Mn+)1/nis a metal cation in which M is a metal and n is 1 or 2, e.g. M is an alkali metal, an alkaline earth metalFor example, M is Li, Na or K, or M is Li and n is 1;
m is an integer selected from 0 or 1;
or a tautomer thereof.
24. The compound of claim 23, wherein X1Is a carbon atom.
25. The compound of claim 24, wherein R8And R9At least one of which is CN or optionally substituted C1-6Alkyl radical
26. The compound of claim 24 or 25, wherein R8And R9Are all CN or optionally substituted C1-6An alkyl group.
27. The compound of claim 24 or 25, wherein R8And R9Are all CN.
28. The compound of claim 24 or 25, wherein R8And R9All fluorine substituted C1-6An alkyl group.
29. The compound of claim 23, wherein X1Is a nitrogen atom.
30. The compound of claim 29, wherein R9Is fluorine substituted SO2Alkyl (e.g. SO)2CF3)。
31. The compound of any one of claims 23-30, wherein m is 0.
32. The compound of any one of claims 23-30, wherein m is 1.
33. The compound of claim 23, wherein the compound is selected from the group consisting of:
or a tautomer thereof.
34. A compound as defined in formula V:
wherein R is1、R2、R8、R9、X1M and n are as previously defined, or R8And R9Is absent, X1Is an oxygen atom;
or a tautomer thereof.
35. The compound of claim 34, wherein R1And R2Is CN.
36. The compound of claim 35, wherein R1And R2Are all CN.
37. A compound according to any one of claims 34 to 36, wherein X1Is a carbon atom.
38. The compound of claim 37, wherein R8And R9At least one of which is CN or optionally substituted C1-6An alkyl group.
39. The compound of claim 37, wherein R8And R9Are all CN or optionally substituted C1-6An alkyl group.
40. The compound of claim 37, wherein R8And R9Are all CN.
41. The compound of claim 37, wherein R8And R9All fluorine substituted C1-6An alkyl group.
42. A compound according to any one of claims 34 to 36, wherein X1Is a nitrogen atom.
43. A compound according to claim 42, wherein R9Is fluorine substituted SO2Alkyl (e.g. SO)2CF3)。
44. The compound of any one of claims 1 to 43, wherein M is Li and n is 1.
45. The compound of claim 34, wherein the compound is selected from the group consisting of:
or a tautomer thereof.
46. Electrode material comprising a compound as defined in any of claims 1 to 45 as additive and at least one electrochemically active material.
47. An electrolyte composition comprising a compound as defined in any one of claims 1 to 45.
48. The electrolyte composition of claim 47, further comprising a compatible solvent.
49. The electrolyte composition of claim 48, wherein the compatible solvent is an organic solvent.
50. The electrolyte composition of claim 48, wherein the compatible solvent is an aqueous solvent.
51. The electrolyte composition of claim 47, further comprising a compatible solvating polymer.
52. An electrochemical cell comprising an electrolyte, an electrode and a counter electrode, wherein at least one of the electrode or counter electrode comprises an electrode material as defined in claim 46.
53. An electrochemical cell comprising the electrolyte of any one of claims 47 to 51, an electrode, and a counter electrode.
54. The electrochemical cell of claim 52 or 53, wherein the electrochemical cell is a battery, an electrochromic device, or a capacitor.
55. The electrochemical cell of claim 54, wherein the battery is a lithium battery or a lithium ion battery.
56. Use of an electrochemical cell according to any one of claims 52 to 55 in an electric or hybrid vehicle or in a ubiquitous IT device.
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CN111342126A (en) * 2020-03-18 2020-06-26 钱起 Method for prolonging service life of electric appliance in high-temperature overvoltage environment
CN111525186A (en) * 2020-04-09 2020-08-11 常州大学 All-solid-state polymer electrolyte based on zwitterionic liquid modified polyvinyl alcohol and preparation method thereof
CN111477962A (en) * 2020-05-29 2020-07-31 珠海市赛纬电子材料股份有限公司 Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte

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